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A Guide To Understanding Reference Electrode Readings PDF
A Guide To Understanding Reference Electrode Readings PDF
Understanding
buried or submerged metallic structure is
cathodically protected (polarized) to a
sufficient degree is based on a measure-
ment of the metal’s polarized potential,
in its environment (soil, seawater, etc.),
Reference
relative to the potential of a reference
electrode. Consequently, no equipment
item is of more fundamental importance
to the cathodic protection (CP) industry
Electrode
than the reference electrode.
There are a number of different refer-
ence electrode types available, including
those that are identified in SP0169-2007,
that are acceptable alternatives to the
Readings
copper/copper sulfate (Cu/CuSO4) ref-
erence electrode (CSE). It is important
for the corrosion engineer to appreciate
the characteristics of the various electrode
types and, in particular, how readings
Robert M. Park, M.C. Miller Co., Inc., Sebastian, Florida taken with different reference electrodes
can be adjusted to the CSE potential.
The purpose of this article is not to
discuss the relative merits of the various
Reference electrodes are essential to evaluate reference electrode types, but to provide
a guide to the corrosion engineer regard-
ing their application. A universal formula
corrosion and cathodic protection on buried and is provided that allows readings taken
with alternative reference electrode types
submerged structures. This article discusses the to be adjusted to the CSE potential.
FIGURE 1
table 1
Expected “native” Fe potential in neutral soil as measured by a variety of reference
electrodes(A)
Voltmeter Potentials of Electrodes
Configuration Involved in Voltage ∆P (Expected Expected Readings Adjusted
(Figure 1) Reading (at 25 °C) Voltage Reading) to the CSE Potential
1 Fe [P = –440 mV] –440 mV – 316 mV = –756 mV N/A
CSE [P = 316 mV]
2 Fe [P = –440 mV] –440 mV – 199 mV = –639 V 199 mV – 316 mV + reading =
Ag/AgCl (sat. KCl) [P = 199 mV] [199 – 316 + (–639)] mV =
–756 mV
3 Fe [P = –440 mV] –440 mV – 244 mV = –684 mV 244 mV – 316 mV + reading =
Calomel (sat. KCl) [P = 244 mV] [244 – 316 + (–684)] mV =
–756 mV
4 Fe [P = –440 mV] –440 mV – (–762 mV) = 322 mV –762 mV – 316 mV + reading =
Zn [P = –762 mV] [–762 – 316 + 322] mV =
–756 mV
Measurements are based on the voltmeter configurations indicated in Figure 1. Also shown are the expected readings adjusted to the CSE
(A)
potential.
table 2
Expected “native” Fe potential in neutral soil as measured by a number of Ag/AgCl reference
electrodes having various molarities of KCl filling solution(A)
Voltmeter Potentials of Electrodes
Configuration Involved in Voltage ∆P (Expected Expected Readings Adjusted
(Figure 2) Reading (at 25 °C) Voltage Reading) to the CSE Potential
1 Fe [P = –440 mV] –440 mV – 316 mV = –756 mV N/A
CSE [P = 316 mV]
2 Fe [P = –440 mV] –440 mV – 199 mV = –639 V 199 mV – 316 mV + reading =
Ag/AgCl (sat. KCl) [P = 199 mV] [199 – 316 + (–639)] mV =
–756 mV
3 Fe [P = –440 mV] –440 mV – 205 mV = –645 mV 205 mV – 316 mV + reading =
Ag/AgCl (3.5 M KCl) [P = 205 mV] [205 – 316 + (–645)] mV =
–756 mV
4 Fe [P = –440 mV] –440 mV – 222 mV) = –662 mV 222 mV – 316 mV + reading =
Ag/AgCl (1.0 M KCl) [P = 222 mV] [–222 – 316 + (–662)] mV =
–756 mV
5 Fe [P = –440 mV] –440 mV – 250 mV = –690 mV 250 mV – 316 mV + reading =
Ag/AgCl (0.5 M KCl) [P = 250 mV] [250 – 316 + (–690)] mV =
–756 mV
Measurements are based on the voltmeter configurations indicated in Figure 2. Also shown are the expected readings adjusted to the CSE
(A)
potential.
table 3
Expected “native” Fe potential as measured by Ag/AgCl elements directly exposed to
seawater and diluted-seawater electrolytes(A)
Voltmeter Potentials of Electrodes
Configuration Involved in Voltage ∆P (Expected Expected Readings Adjusted
(Figure 3) Reading (at 25 °C) Voltage Reading) to the CSE Potential
1 Fe [P = –440 mV] –440 mV – 316 mV = –756 mV N/A
CSE [P = 316 mV]
2 Fe [P = –440 mV] –440 mV – 250 mV = –690 V 250 mV – 316 mV + reading =
Ag/AgCl (seawater) [P = 250 mV] [250 – 316 + (–690)] mV =
–756 mV
3 Fe [P = –440 mV] –440 mV – 370 mV = –810 mV 370 mV – 316 mV + reading =
Ag/AgCl (<1% seawater) [370 – 316 + (–810)] mV =
[P = 370 mV] –756 mV
Measurements are based on the voltmeter configurations indicated in Figure 3. Also shown are the expected readings adjusted to the CSE
(A)
potential.
the potential of the reference electrode in of the voltmeter connects to the metal by a CP system to, say, 100 mV above
use), expected readings can be deter- under test, which is Fe in the example the native potential, the effective Fe po-
mined. As the table illustrates, since the shown, and the negative side of the volt- tential will be –540 mV vs. SHE and the
potentials of the various reference elec- meter connects to the reference electrode. “instant-off” voltage reading will be –856
trodes are different from each other, For a given reference electrode in use, for mV vs. CSE (–540 mV minus 316 mV).
different Fe potentials are expected vs. example a CSE, the potential value of the
the different reference electrodes. metal under test will determine the volt- Universal Adjustment
All of the voltage reading values shown age reading. As indicated in Table 1, a Formula
in Table 1 (and also in Tables 2 and 3) “native” Fe potential of –440 mV vs. SHE As the tables indicate, voltage readings
correspond to a particular voltmeter will yield a voltage reading of –756 mV taken vs. a non-CSE reference electrode
configuration—namely, the positive side vs. CSE. If, however, the Fe is polarized can be adjusted to the CSE potential.
34 MATERIALS PERFORMANCE September 2009
FIGURE 2